Chemical Engineering Journal xxx (xxxx) xxx–xxx

Contents lists available at ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Impact of synthesis conditions on Pb(II) removal efficiency from aqueous

solution by green tea extract reduced graphene oxide
⁎
Xiulan Wenga, Jing Wua, Li Maa, Gary Owensb, Zuliang Chena,
a
School of Environmental Science and Engineering, Fujian Normal University, Fuzhou 350007, Fujian Province, China
b
Environmental Contaminants Group, Future Industries Institute, University of South Australia, Mawson Lakes, SA 5095, Australia

H I GH L IG H T S

• GO was biogenically reduced to RGO by a green tea extract.

• Pb(II) removal efficiency was related to GO reduction conditions.
• Highest Pb(II) removal (97.2%) by RGO occurred.
• This study provides new insights into the mechanism of GO reduction.

A R T I C LE I N FO A B S T R A C T

Keywords: Graphene has a great potential in environmental remediation due to its unique physical and chemical properties.
Green reduction However, the relationships between synthetic conditions and contaminant removal are still unclear. In this
RGO study, a biogenic method was used for the reduction of graphene oxide (GO) using green tea extract and the
Green tea extract reduced graphene oxide (RGO) produced was subsequently used to remove Pb(II) from aqueous solution. Hence,
Pb(II)
the impact of bioreduction synthetic conditions of RGO on Pb(II) removal efficiency was examined. The new
Removal
findings included (1) that reduction of GO by green tea (GT) extract at a ratio of 2:1 (GO:GT), 80 °C and pH 8, led
to a RGO material capable of removing 97.2% of a 10 mg·L−1 Pb(II) solution under the adsorption conditions of
pH 4.5 and a RGO dose of 0.4 g·L−1 at 30 °C; (2) characterization results showed good dispersion of RGO, and
removal of oxygen functional groups from GO, increased Pb(II) adsorption. Pb(II) removal efficiency was largely
dependent on reduction conditions during synthesis of RGO; where efficient removal of oxygen-containing
groups during reduction favored Pb(II) removal. Furthermore, during biogenic synthesis RGO was also capped
by biomolecules such as polyphenols which decreased aggregation leading to enhanced Pb(II) removal effi-
ciency.

1. Introduction contaminated water [3–5]. However, amongst these, adsorption is now

commonly recognized as the most effective, facile and economic
Heavy metals in wastewater have become a key environmental issue method for treatment of heavy metals in wastewater because adsorp-
because of their toxicity, bioaccumulation and persistence [1]. As trace tion often has the advantage of being reversible, so that adsorbents can
elements, heavy metals such as copper, selenium and zinc are all es- be regenerated by a suitable desorption process and reused [4–6].
sential to maintain the metabolism of the human body. However, some Graphene is a flat monolayer of sp2 hybridized carbon atoms ar-
heavy metals can pose a serious threat to public health and ecosystems, ranged in a honeycomb lattice, which has received significant attention
even at very low concentrations due to bioaccumulation and bio-mag- in the scientific community worldwide due to its unique physiochem-
nification [2]. Previously, a variety of methods, including adsorption, ical properties [7]. Consequently, the application of graphene and its
chemical precipitation, electrochemical treatment, electro dialysis, derivatives in adsorption processes is being widely explored and re-
evaporative recovery, filtration, ion-exchange, membrane technologies, cently numerous reports have described the utilization of graphene and
oxidation/reduction, reverse osmosis, solvent extraction and ultra-fil- its composites as good adsorbents for the removal of dyes and heavy
tration, have all been proposed to separate heavy metal ions from metal ions from aqueous solutions [8–10]. Magnetic graphene could

⁎
Corresponding author.
E-mail address: [email protected] (Z. Chen).

https://doi.org/10.1016/j.cej.2018.11.089
Received 3 August 2018; Received in revised form 18 October 2018; Accepted 11 November 2018
1385-8947/ © 2018 Published by Elsevier B.V.

Please cite this article as: Weng, X., Chemical Engineering Journal, https://doi.org/10.1016/j.cej.2018.11.089
X. Weng et al. Chemical Engineering Journal xxx (xxxx) xxx–xxx

also be an effective adsorbent for As(V), Cr(VI) and Pb(II) and is a by sonication for 1 h. A green tea extract was prepared by heating a
preferred adsorbent for producing safe drinking water [11]. Super- mixture of green tea (5 g) and deionized water (500 mL) in an 80 °C
hydrophobic and superhydrophylic hybrid foams of graphene and water bath for 1 h, prior to filtering through a 0.45 μm cellulose acetate
carbon nanotubes were recently used for selective removal of oils and membrane. Aliquots of green tea extracts (GT) were then combined
organic solvents from surface water [12]. However, application of such with the GO dispersions, and heated in a water bath at 80 °C for 8 h.
toxic reducing agents for large scale remedial applications is potentially After reaction the RGO was filtered by a 0.45 μm cellulose acetate
hazardous to both human and ecosystem health [7]. Thus to minimize membrane and washed three times sequentially with ethanol and DI-
environmental impacts, the production of natural/non-toxic reducing water to remove any impurities. The synthesis was repeated multiple
agents have been investigated. One such alternative is the green times at different pH (2, 5, 8, 11), where the pH was adjusted by either
synthesis of biomaterials which have been widely used in environ- HCl or NaOH solution (0.1 M), temperature (70, 80, 90 °C) and at dif-
mental remediation. For example, iron nanoparticles green synthesed ferent ratios of GO to GT (3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6).
by various tea extracts degraded malachite green [13,14] and iron
nanoparticles derived from either green tea or eucalyptus leaf extracts 2.3. Characterization
removed nitrate from aqueous solution [15]. Hence, plant based ex-
tracts such as leaves from various plants may provide green alternatives The size distribution and morphologies of the produced samples
to replace existing toxic reducing agents currently used for GO reduc- were characterized using a Scanning Electron Microscope-Energy
tion. Dispersive Spectrometer (SEM-EDS) on a S4800 (Hitachi Limited
Several green methods have been reported for the reduction of GO Japan). Surface composition was examined using X-ray photoelectron
using various green reagents like alkaloids, alcoholic derivatives, amino spectroscopy (XPS) on an Escalab 250Xi (Thermo Escalab, USA) mul-
acids, chelating agents, enzymes, polyphenolic compounds, proteins, tifunctional imaging photoelectron spectrometer with monochromatic
polysaccharides and vitamins [16]. Although the reduction efficiency Al Kα radiation at 1486.6 eV. The type of functional groups present on
obtained through green methods is usually lower than that obtained the surface of the samples were characterized using Fourier transform
with conventional chemical methods, green reduction processes are infrared spectroscopy (FT-IR) on fine powders pressed into KBr plates
widely accepted and understood as being common natural practices in and collected on a Thermo Fisher Nicolet 10 spectrometer (USA) in the
the biological and biomedical fields. Most of the current reported green range of 400–4000 cm−1. Thermal degradation behavior of both pris-
methods are not optimal for large scale production and suffer from tine GO, and RGO were determined via Thermogravimetric Analysis
several limitations including (1) relatively long synthesis times (TGA) on a thermal analyzer, Q500 (TA Instruments, America) with a
(e.g.48–72 h) [17], (2) relatively poor product stability [18,19] and (3) nitrogen flow rate of 50 mL·min−1 and a heating rate of 10 °C·min−1.
poor solubility (e.g. < 0.1 mg·mL−1) [20] which generally makes pre-
paration of large quantities of RGO and long-term storage difficult. 2.4. Batch adsorption experiments
While extensive work has already been performed on the biogenic
synthesis of RGO [7,8], few reports have considered how the adsorption Analytical-grade lead nitrate was initially used to prepare two Pb(II)
of metal ions using RGO, is influenced by the synthetic conditions used stock solutions, at concentrations of either 10 or 30 mg·L−1. The Pb(II)
to produce RGO. To address this issue, in this work, a biogenic “green” adsorption efficiency for several absorbents including GT, commercial
reduction method was employed to produce RGO under different syn- graphene (C-RGO), GO and RGO, were carried out in Erlenmeyer flask.
thetic conditions and subsequently the ability of the produced RGO to A sample of dried and powdered materials (60 mg) was weighed into a
adsorb Pb(II) was evaluated. Therefore, the following aspects were 250 mL Erlenmeyer flask and either 10 or 30 mg·L−1 Pb(II) solution
studied (1) characterization of GO and RGO; (2) the removing of Pb(II) (150 mL) were added, respectively. Equilibrium batch adsorption ex-
with different materials; (3) the effect of different reduction RGO periments for Pb(II) adsorption onto RGO obtained under a variety of
conditions on Pb(II) removal efficiency. different synthetic conditions were also examined using the same batch
adsorption experiments where a 10 mg·L−1 Pb(II) solution (150 mL)
2. Experimental added.
All adsorption experiments were performed at 30 °C and at pH 4.5;
2.1. Materials which was obtained via adjustment of the initial pH by the addition of
negligible amounts of 0.1 M HNO3 or NaOH. The suspensions were then
Graphite powder was purchase from Aladdin Co., Ltd. Shanghai, shaken on a TY-R70B shaker (Tianjin, China) at 250 rpm for the se-
China. Potassium permanganate (KMnO4) was obtained from Tianjin lected time intervals. Thereafter the solid phase was separated from the
Bodi Chemical Co., Ltd. (Tianjin, China). Sulfuric acid was purchased solution phase using 0.22 mm membrane filters and the residual Pb(II)
from Hunan Kaixin Chemical reagent Co., Ltd. (Hunan, China). concentration in the solution was determined by atomic absorption
Hydrogen peroxide (H2O2, 30%), concentrated hydrochloric acid and spectroscopy (AAS), at 283.3 nm and a lamp current of 6 mA. The
ethyl alcohol were purchased from Tianjin Guanghua Science and amount of metal ions adsorbed was calculated as follows:
Technology Co. Ltd (Tianjin, China). Lead nitrate was obtained from
C0 − Ce
Sinopharm Chemical Reagent Co., Ltd (Shanghai, China). Green tea was η= × 100%
C0 (1)
supplied by Hangzhou Yijiangnan Tea Industry Co., Ltd. All chemical
regents were of analytical grade and were used as received. Deionized where η (%) was the Pb(II) removal efficiency, C0 was the initial Pb(II)
water was used in all experiments. concentration (mg·L−1) and Ce was the equilibrium Pb(II) concentra-
tion after reaction (mg·L−1). All experiments were undertaken in du-
2.2. Preparation of reduced graphene oxide plicate.

Green tea was used here as a biogenic reducing agent because it is 3. Results and discussion
one of the most popular beverages worldwide and is a rich source of
polyphenolic compounds; where efficient biogenic reduction is com- 3.1. Characterization
monly attributed to such antioxidant chemicals (mainly polyphenols)
being present in green tea extracts [16]. The SEM images Fig. 1a revealed that GO consisted of individual
Graphene oxide was prepared from graphite powder using a mod- sheets closely associated with each other [22], with a silky and leaf-like
ified Hummers’ method [21]. GO (0.5 g) was dispersed in DI-water (1 L) structure. In comparison RGO displayed an aggregated structure with

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Fig. 1. The SEM images of (a) GO and (b) RGO.

Fig. 2. EDX spectrum of GO (a) and RGO (b).

fully inflated curliness (Fig. 1b), that may be due to self-assembly via peak at 3400 cm−1 observed for GO is attributed to the stretching vi-
Vander Waals' force during reduction, the surfaces are coarse and hairy, brations of hydroxyl groups [24]. The peak at 1732 cm−1 shows the
and the edges of the flakes blurry [22]. The degree of stacking was presence of a keto C]O stretching vibration, as well as a C]O bending
improved significantly by polyphenols and caffeine because of the fa- vibration peak at 1622 cm−1, epoxy CeO stretching vibration peak at
vorable dispersibility of green tea extracts. 1224 cm−1 and a alkoxy CeOH stretching peak at 1053 cm−1 [25].
Elemental composition of RGO was determined by EDS. As shown in After reduction of GO with green tea, the peaks belonging to carbonyl
Fig. 2a, the synthesized GO contained both C (56.5%) and O (26.5%) C]O group are diminished and the peaks related to epoxy and keto
peaks. In comparison, RGO (Fig. 2b) contained larger amounts of groups are also almost entirely eliminated. The peaks at 1618 cm−1 and
carbon (71.7%) relative to oxygen (20.6%). This confirmed the suc- 3386 cm−1 in RGO are attributed to C]C skeleton vibrations and the
cessful green synthesis of RGO using green tea extract since the number OeH stretching vibration, respectively. The FTIR spectra of RGO ob-
of oxygen-containing functional groups was reduced. In addition, the tained here was almost identical with that of hydrazine reduced RGO
percentage of Si still exists because of the silica composition as the reported earlier [25].
substrate [2]. The thermal stability of GO and RGO were examined by TGA
XPS was also used to determine the elemental composition of RGO (Fig. 5). It is known that GO is thermally unstable, and heating of GO
and simultaneously estimate the reduction level of GO [7,23]. The powder at a high temperature can result in the loss of mass due to the
presence of the O1s peak along with the C1s peak in the XPS survey elimination of oxygen groups [26]. Thus for GO, the first weight loss of
spectrum of GO (Fig. 3a) confirmed harsh oxidation of graphite to GO. 25.4% commenced at 110 °C and followed by another 23.4% at 200 °C
After reduction by the green tea extract, the C/O ratio increased sig- due to the loss of hydroxyl, epoxy functional groups and any remaining
nificantly from 2.01 to 3.04, indicating that the oxygen-containing water molecules. The second step degradation occurred at 400 °C which
groups of GO had indeed been removed. Fig. 3b shows the typical raw involved the pyrolysis of the remaining oxygen-containing groups as
and de-convoluted peaks at 284.6, 285.4, 286.5, and 288.2 eV. The well as the burning of ring carbon [27]. In comparison, RGO lost only
peak at 284.6 corresponds to C]C in the aromatic rings. The other 12.2% mass up to 200 °C, and a 55.1% mass lose after 200 °C. This
three peaks centered at the binding energies of 285.4, 286.5, and indicated that the oxygen containing functional groups which had ex-
288.2 eV are assigned to the CeC, CeO, C]O. Fig. 3c illustrates the C1s tensively decorated GO had been effectively removed by GT reduction.
XPS spectrum of RGO, where peaks at 284.7, 285.7, 286.8, 287.8 eV, The observed thermal stability of green reduced RGO is also well in
are attributed to the C]C, CeC, CeO, C]O bonds. The intensities of agreement with the reported literature values [25].
oxygen group peaks decreased dramatically, especially for carbonyl
groups (C]O), hydroxyl and epoxy groups (CeO). And CeC aromatic
3.2. The removing of Pb(II) with different materials
lattice peak intensity increased in RGO. Therefore, green tea extract
was a potentially environmentally friendly reductant for effectively
The removal efficiency of Pb(II) varied with both time and the ad-
converting GO to RGO.
sorption material tested (Fig. 6). At equilibrium for an initial Pb(II)
FT-IR spectra of GO and RGO are shown in Fig. 4. The strong broad
concentration of 10 mg·L−1, the removal efficiency of Pb(II) by GT, C-

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Fig. 3. XPS survey spectra overlay of GO and RGO (a) and separate detailed C1s spectra of GO (b) and RGO (c).

Fig. 5. The TGA curves of GO and RGO.

Fig. 4. The FT-IR spectra of GO and RGO.

attributed in part to functional groups in tea extract; such as eCOOH
and eOH, being complexed with Pb(II) [13–15]. A much higher re-
RGO, GO, and RGO was 14.5, 19.8, 87.0 and 96.1%, respectively
moval efficiency for Pb(II) was obtained by GO. According to the results
(Fig. 6a). Similarly, while lower, the removal efficiency of Pb(II) at
of characterization by EDS, XPS, FT-IR and TG, this most likely resulted
30 mg·L−1 by GT, C-RGO, GO, and RGO retained the same trend being
directly from the high hydroxyl content located along the edges of GO,
6.9, 12.6, 40.0 and 73.9%, respectively (Fig. 6b). It is noteworthy that
where such negatives charge can interact strongly to adsorb cationic Pb
the Pb(II) removal efficiency of C-RGO was relatively poor at only 19.8
(II). However, the highest removal efficiency for Pb(II) was 96.1 and
and 12.6%, respectively for initial Pb(II) concentrations of 10 and
73.9% for initial Pb(II) concentrations of 10 or 30 mg·L−1, respectively
30 mg·L−1, indicating poor Pb(II) adsorption by C-RGO. Similarly, the
by RGO. This was despite the results of EDS, XPS, FT-IR and TG analysis
removal efficiency of Pb(II) by GT was only 14.5 and 6.9%, for initial
suggesting that the hydroxyl content of RGO was lower than that of the
Pb(II) concentrations of 10 and 30 mg·L−1, respectively, which was
parent GO. Thus the presence of hydroxyl groups by themselves is not

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Fig. 6. Temporal variation of Pb(II) removal efficiency with four different materials studied at two initial Pb(II) concentrations. C[Pb(II) initial] = 10 mg·L−1 (a) or
30 mg·L−1 (b).

solely responsible for increasing Pb(II) adsorption. It is clear then that

the total conjugated structure of the material has some significant effect
on increasing the absorbability of RGO for Pb(II). This may result from
a combination of RGO’s increased ability to donate electron for Pb(II)
complexation and an increase in the concentration of GT increased
concentrations of GT derived biomolecules coating the biogenic RGO
surface [25]. Previous studies have indicated that at high pH graphene
can exhibit enhanced Lewis base characteristic resulting in increased
formation of donor acceptor complexes between RGO and Pb(II) in
aqueous solution [10]. Since the adsorption of GO increased sig-
nificantly after reduction by GT, biogenically derived RGO has sig-
nificant advantages over GT, GR and GO for Pb(II) adsorption [10].

3.3. Effect of different conditions on Pb(II) removal efficiency

Although adsorption equilibrium was reached within 30 min, the

equilibrium removal efficiency of Pb(II) by RGO was dependent on the
GO:GT ratio (1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1) used to prepare the
final material (Fig. 7a). The best Pb(II) removal efficiency (96.1%)
occurred for a GO:GT of 2:1. As the amount of GT decreased, the
concentration of active ingredient from GT would also decrease leading
directly to a decrease in the degree of reduction of RGO and an increase
in residual oxygenic groups. Reduction of oxygen containing groups in
GO by tea polyphenols and caffeine in green tea extracts is known to
significantly increase both hydrophilicity and adsorption performance
[28]. Thus for a fixed dose of RGO and a constant Pb(II) concentration,
decreases in GT and hence polyphenol concentration, would have re-
sulted in a decreased degree of reduction of GO to RGO and con-
sequentially a decrease in Pb(II) removal efficiency by the final material
produced.
During material synthesis, the reduction temperature also influ-
enced the Pb(II) removal efficiency of the final RGO material produced
(Fig. 7b). While the removal efficiency of Pb(II) using RGO at reduction
temperatures of 80 and 90 °C were similar, being 96.1 and 96.9% re-
spectively, both were much higher than removal efficiency observed
using RGO produced at a reduction temperature of 70 °C (only 90.7%).
While higher temperatures are generally known to increase the rate of
reduction [8,23], the results obtained here indicated that above 80 °C
there was no significant benefit in the final Pb(II) removal efficiency.
During reduction, graphene is an ideal nonporous adsorbent, and ad-
sorption mainly occurs on its planar surface which is only controlled by
external diffusion [29]. During reduction, the reducing agents assist in
the removal of the oxygen-containing functional groups from the GO
surface in order to fully restore electronic conjugation of the honey-
comb lattice [7]. The higher removal efficiency was thus attributed to
more available active sites following restoration of electronic con- Fig. 7. Effect of GO:GT ratios (a), RGO reduction temperature (b) and pH (c) on
jugation. the removal efficiencies of Pb(II) by the RGO produced over time.
The variation in Pb(II) removal efficiency by RGO with pH is shown
in Fig. 7c. The highest Pb(II) removal efficiency (97.2%) was observed

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